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Magnetocaloric effect and refrigerant capacity in charge-ordered manganites

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The influence of first- and second-order magnetic phase transitions on the magnetocaloric effect (MCE) and refrigerant capacity (RC) of charge-ordered Pr0.5Sr0.5MnO3 has been investigated. The system undergoes a paramagnetic to ferromagnetic transition at TC∼255 K followed by a ferromagnetic charge-disordered to antiferromagnetic charge-ordered transition at TCO∼165 K. While the first-order magnetic transition (FOMT) at TCO induces a larger MCE (6.8 J/kg K) limited to a narrower temperature range resulting in a smaller RC (168 J/kg), the second-order magnetic transition at TC induces a smaller MCE (3.2 J/kg K) but spreads over a broader temperature range resulting in a larger RC (215 J/kg). In addition, large magnetic and thermal hysteretic losses associated with the FOMT below TCO are detrimental to an efficient magnetic RC, whereas these effects are negligible below TC because of the second-order nature of this transition. These results are of practical importance in assessing the usefulness of charge-ordered manganite materials for active magnetic refrigeration, and Pr0.5Sr0.5MnO3 provides an interesting case study in which the influence of first- and second-order transitions on MCE could be compared in the same system in a single experiment.
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Magnetocaloric effect and refrigerant capacity in charge-ordered manganites
N. S. Bingham, M. H. Phan, H. Srikanth, , M. A. Torija, and C. Leighton
Citation: Journal of Applied Physics 106, 023909 (2009); doi: 10.1063/1.3174396
View online: http://dx.doi.org/10.1063/1.3174396
View Table of Contents: http://aip.scitation.org/toc/jap/106/2
Published by the American Institute of Physics
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Magnetocaloric effect and refrigerant capacity in charge-ordered
manganites
N. S. Bingham,1M. H. Phan,1H. Srikanth,1,aM. A. Torija,2and C. Leighton2
1Department of Physics, University of South Florida, Tampa, Florida 33620, USA
2Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis,
Minnesota 55455, USA
Received 11 April 2009; accepted 11 June 2009; published online 17 July 2009
The influence of first- and second-order magnetic phase transitions on the magnetocaloric effect
MCEand refrigerant capacity RCof charge-ordered Pr0.5Sr0.5MnO3has been investigated. The
system undergoes a paramagnetic to ferromagnetic transition at TC255 K followed by a
ferromagnetic charge-disordered to antiferromagnetic charge-ordered transition at TCO165 K.
While the first-order magnetic transition FOMTat TCO induces a larger MCE 6.8 J/kg Klimited
to a narrower temperature range resulting in a smaller RC 168 J/kg, the second-order magnetic
transition at TCinduces a smaller MCE 3.2 J/kg Kbut spreads over a broader temperature range
resulting in a larger RC 215 J/kg. In addition, large magnetic and thermal hysteretic losses
associated with the FOMT below TCO are detrimental to an efficient magnetic RC, whereas these
effects are negligible below TCbecause of the second-order nature of this transition. These results
are of practical importance in assessing the usefulness of charge-ordered manganite materials for
active magnetic refrigeration, and Pr0.5Sr0.5MnO3provides an interesting case study in which the
influence of first- and second-order transitions on MCE could be compared in the same system in a
single experiment. © 2009 American Institute of Physics.DOI: 10.1063/1.3174396
I. INTRODUCTION
Doped manganites with a general formula of
R1−xMxMnO3R=La, Pr, Nd, etc., and M=Sr, Ca, Ba, etc.
exhibit a rich variety of phenomena such as colossal
magnetoresistance1and large magnetocaloric effect MCE.2
The latter effect, which is represented by an isothermal
change in magnetic entropy or an adiabatic change in tem-
perature in magnetic fields, forms the basis for magnetic
refrigeration.3Manganites are relatively easy to synthesize,
are tunable by adjustment of the doping concentration, and
are considered promising candidates for magnetic refrigera-
tion at various temperatures, as reviewed by Phan and Yu.2
Recently, half-doped R0.5M0.5MnO3manganites that ex-
hibit a giant magnetic entropy change SMin the vicinity
of the charge-ordered COtransition have attracted
attention.49Sande et al.4reported values of SM
2.8 J/kg K in Nd0.5Sr0.5MnO3around the antiferromag-
netic AFMCO to ferromagnetic FMcharge-disordered
transition temperature, TCO the first-order magnetic transi-
tion FOMT兲兴, which was about three times larger than that
0.9 J/kg Kobtained around the paramagnetic to FM transi-
tion temperature, TCthe second-order magnetic transition
SOMT兲兴, for a field change of 1 T. A similar trend has also
been observed in other CO manganites.59This leads to a
general expectation that the consistently larger values of SM
around TCO would be more useful for magnetic refrigeration
than those around TC.
However, in assessing the usefulness of a magnetic re-
frigerant material, the refrigerant capacity RC, which is a
measure of the amount of heat transfer between the cold and
hot sinks in an ideal refrigeration cycle, is considered to be
the most important factor.1012 The RC depends not only on
the magnitude of SM, but also on the temperature depen-
dence of SMe.g., the full width at half maximum of the
SMTpeak.10,12 In this context, a good magnetic refriger-
ant material with large RC requires both a large magnitude of
SMas well as a broad width of the SMTcurve. Most
previous studies on CO manganites49were focused mainly
on exploring large MCE large magnitudes of SMaround
TCO and did not consider in detail the issues of RC and
hysteretic losses. Thus, from fundamental and practical per-
spectives, it is essential to understand the influence of the
magnetic phase transitions on both the MCE and RC in these
materials.
In this paper, we present systematic studies of the influ-
ence of the FOMT and SOMT on the MCE and RC of CO
Pr0.5Sr0.5MnO3. Our results reveal that while the FOMT at
TCO induces a larger MCE, it is restricted to a narrow tem-
perature range resulting in a smaller RC. The SOMT at TC
induces a smaller MCE but with a distribution over a broader
temperature range, thus resulting in a larger RC. In addition,
hysteretic losses associated with the FOMT are very large
below TCO and therefore detrimental to the RC, whereas
these effects are very small or negligible below TCdue to the
nature of the SOMT.
II. THEORETICAL BACKGROUND
The change in the entropy Sof a magnetic material in
a magnetic field His related to that of magnetization M
with respect to temperature Tthrough the thermodynamic
Maxwell relation,
aElectronic mail: sharihar@cas.usf.edu.
JOURNAL OF APPLIED PHYSICS 106, 023909 2009
0021-8979/2009/1062/023909/5/$25.00 © 2009 American Institute of Physics106, 023909-1
ST,H
H
T
=
MT,H
T
H
.1
The change in magnetic entropy, SM, caused by the varia-
tion in applied magnetic field from 0 to H0, is calculated as
SMT,H0=SMT,H0SMT,0
=
0
0
H0
MT,H
T
H
dH,2
with
0being the permeability in vacuum. For magnetization
measurements made at discrete field and temperature inter-
vals, SMcan be approximately calculated as
SMT,H0=
0
i
Mi+1Ti+1,HMiTi,H
Ti+1 Ti
H.3
On the other hand, SMcan be obtained from calorimet-
ric measurements of the field dependence of the heat capac-
ity and subsequent integration,
SMT,H0=
0
TCT,HCT,0
TdT,4
where CT,H0and CT,0are the values of the heat capac-
ity measured in the field H0and in zero field H=0, respec-
tively. Therefore, the adiabatic temperature change Tad
can be evaluated by integrating Eq. 4over the magnetic
field, which is given by
TadT,H0=
0
0
H0
T
CT,H
MT,H
T
H
dH.5
By taking Eq. 2into account, the adiabatic temperature
change Tadat an arbitrary temperature T0can be approxi-
mately calculated by
TadT0,H0兲⬵SMT0,H0T0
CT0,H0.6
The RC of a magnetic refrigerant material is calculated as10
RC = −
T1
T2
SMTdT,7
which indicates how much heat can be transferred from the
cold end at T1to the hot end at T2of a refrigerator in an
ideal thermodynamic cycle.
We note from Eq. 2that the magnitude of SMdepends
on both the magnitude of the magnetization Mand
M/
TH. The larger these values, the larger the magnitude
of SM.13 Since
M/
THis related to the magnetic order-
ing transition, the sharper change in Mwith respect to tem-
perature at the transition temperature leads to the larger
SM.14,15 According to Eq. 6, at the same temperature the
large Tad is achieved as the SMis large and the CT,His
small. Since the magnitude of CT,Hvaries from one ma-
terial to another, large SMdoes not necessarily lead to the
large Tad.10 Therefore, only using the magnitude of SMto
assess the usefulness of a magnetic refrigerant material is
inadequate. Instead, a more appropriate way to do this is to
calculate the RC from Eq. 7, which takes into account both
the magnitude of SMand the temperature response of
SM.1012
III. EXPERIMENT
Polycrystals of Pr0.5Sr0.5MnO3were fabricated from
Pr2O3, SrCO3, and MnO using standard solid-state reaction
methods. The starting powders were thoroughly ground and
then reacted in air for 10 days at 1500 °C with several in-
termediate grindings. The reacted powders were then cold
pressed into disks of 1.5 mm thickness and sintered in air for
1 day at 1500 ° C. The final sintered samples were slow
cooled over a period of 40 h to room temperature. Structural
characterization was performed by x-ray powder diffraction,
confirming structure orthorhombicand lattice parameters
similar to those in prior work.
Magnetic measurements were performed using a com-
mercial Physical Property Measurement System from Quan-
tum Design in the temperature range of 5–300 K at applied
fields up to 7 T. The magnetization isotherms were measured
with a field step of 0.05 mT in the range of 0–5 T and with a
temperature interval of 3 K over a temperature range of
5–300 K.
IV. RESULTS AND DISCUSSION
Figure 1ashows the temperature dependence of zero-
field-cooled ZFCand field-cooled FCmagnetizations
FIG. 1. Color online兲共aTemperature dependence of ZFC and FC magne-
tizations taken at a field of 0.05 T. The inset shows the derivative of mag-
netization with respect to temperature dM/dT vs T. The values of TC
255 K and TCO 165 K are, respectively, defined by the minimum and
maximum in dM/dT. AFM/CO, FM, and PM paramagnetic.bTempera-
ture dependence of magnetization taken at different magnetic fields up to 5
T.
023909-2 Bingham et al. J. Appl. Phys. 106, 023909 2009
taken at a field of 0.05 T. In agreement with prior studies,5,6
the present Pr0.5Sr0.5MnO3system undergoes a SOMT from
the paramagnetic to the FM state at TC255 K followed by
a FOMT from the FM charge-disordered to AFM CO state at
TCO 165 K. These transitions are well known in this mate-
rial although the values of TCand TCO extracted from the
minimum and maximum in dM/dT see inset of Fig. 1a,
respectively, are slightly different from those reported in the
literature.5,16 The slightly depressed Curie temperature could
be accounted for by small nonstoichiometry, particularly
oxygen deficiency. It is also noted that Pr0.5Sr0.5MnO3is not
a usual checkerboard type CO antiferromagnet like the case
of Nd0.5Sr0.5MnO3but shows a two-dimensional anisotropic
AFM and charge ordering insulating state.17
The effect of magnetic field on the SOMT and FOMT
are further revealed from MFCTcurves taken in higher
magnetic fields
0H=1,2,3,4,and5T, as shown in Fig.
1b. It can be observed that the SOMT at TCprogressively
broadens as the magnetic field is increased, whereas the
FOMT at TCO remains reasonably sharp even at a field of up
to 5 T due to the strong coupling between the magnetism and
the lattice in the vicinity of the TCO.16 In a study reported by
Hu et al.,14 the compound MnAs0.9Sb0.1 displayed a smooth
temperature variation of the magnetization under high fields,
whereas the shape of the M-Tcurve for MnAs was almost
unchanged. As a result, MnAs exhibited a larger MCE com-
pared with MnAs0.9Sb0.1.14 In a recent study reported by
Phan et al.,18 giant MCE has been observed in a type-VIII
Eu8Ga16Ge30 clathrate in which the SOMT remains quite ro-
bust under high magnetic fields. Our experimental observa-
tion reported here leads to a similar expectation that the
Pr0.5Sr0.5MnO3manganite would show a larger change in
magnetic entropy at around TCO than around TC.
In order to evaluate the MCE, the isothermal magnetiza-
tion curves of the sample were measured with a field step of
0.05 mT in a range of 0–5 T and a temperature step of 3 K
over a range of temperatures around TCand TCO. Such fami-
lies of MHcurves are shown in Figs. 2aand 2b, respec-
tively. As expected from Fig. 1, there is a more drastic
change in the magnetization around the TCO see Fig. 2b
than around the TCsee Fig. 2a, indicating a larger mag-
netic entropy change in the vicinity of the TCO. It is worth
mentioning that around the TCO the sample shows S-shaped
magnetization, which is typical for metamagnetic
materials.19 The importance of metamagnetism for achieving
large MCE in La0.7Ca0.3−xSrxMnO3−
; manganites has re-
cently been discussed by Ulyanov et al.20 The authors have
demonstrated the role of oxygen deficiency as a driving force
for the metamagnetism and large low-field MCE in these
manganites.20 For the case of Pr0.5Sr0.5MnO3, however, it is
believed that the metamagnetism arises mainly from the co-
existence of the competing AFM/CO and FM phases and the
collapse of the AFM/CO state that occurs in the presence of
an external magnetic field.16
Figure 3shows the temperature dependence of the mag-
netic entropy change SMtaken at different magnetic
fields ranging from 0.15 to 5 T. Here, the −SMwas calcu-
lated from a family of isothermal MHcurves shown in
Figs. 2aand 2busing Eq. 2. It can be observed that the
Pr0.5Sr0.5MnO3system exhibits large magnetic entropy
changes around the TCand around the TCO. As expected from
the MTand MHdata, the −SMaround TCO is much
larger than that around TC. For
0H=5 T, the magnitude
of −SM−7.5 J /kg Kat TCO is about twice larger than that
3.2 J/kg Kat TC. A similar trend was also reported by
Sande et al.4on Nd0.5Sr0.5MnO3and by Chen et al.5on
Pr0.5Sr0.5MnO3. In those cases, however, attention was drawn
only to large values of −SMaround TCO without any con-
sideration of the RC and hysteretic losses.4,5In the present
case, we note from Fig. 4that the large −SMaround the TCO
is only sustained over a narrow temperature range, whereas
the −SMaround the TCis spread over a broader temperature
range. This would lead to improved RC, which is the most
important factor for assessing the usefulness of a magnetic
refrigerant material.
FIG. 2. Color onlineIsothermal magnetization curves taken at different
fixed temperatures between 5 and 300 K for the Pr0.5Sr0.5MnO3manganite:
aaround TCand baround TCO.
FIG. 3. Color onlineTemperature dependence of magnetic entropy change
SMat different applied fields up to 5 T for the Pr0.5Sr0.5MnO3
manganite.
023909-3 Bingham et al. J. Appl. Phys. 106, 023909 2009
To address this unresolved important issue, we have cal-
culated the RC for both the cases around the TCand around
the TCO using Eq. 7. Figure 4shows the method for calcu-
lating the RC from the −SMTcurve. In this figure, the
hatched area under the −SMTcurve corresponds to the
RC of the material in each temperature range around TCand
TCO. The upper and lower temperature limits of the shaded
area represent the temperatures of the hot and cold reservoirs
T2and T1, respectively. These limiting temperatures are
obtained from the temperatures at the half maximum of the
peak value of the −SMTcurve.12 The calculated results of
RC are plotted as a function of magnetic field and are shown
in Fig. 5. It can be observed that for both cases, the RC
increases as the magnetic field is increased. An important
fact to be emphasized here is that the magnitude of RC is
significantly larger for the case around the TCthan for the
case around the TCO for
0H3.7 T, which can be con-
sidered as the magnetic field range of practical importance
for refrigeration. For example, for
0H=2 T, the RC is 79
J/kg for the case around the TC, while it is 70 J/kg for the
case around the TCO. As shown previously in Ref. 10,inthe
same refrigeration cycle, a material with higher RC is pre-
ferred because it would support the transport of a greater
amount of heat in a practical refrigerator. Therefore, for the
case of Pr0.5Sr0.5MnO3, the larger value of RC around the TC
indicates that magnetic refrigeration in the vicinity of the TC
is more effective than that around the TCO.
Furthermore, we recall that hysteretic losses magnetic
and thermal hysteresesare often involved in FOMT,19 which
would again justify the calculated RC values. Because these
hysteretic losses are the costs in energy to make one cycle of
the magnetic field, they must be considered when calculating
the usefulness of a magnetic refrigerant material being sub-
jected to field cycling.11 To evaluate possible hysteretic
losses involved in the magnetic phase transitions in
Pr0.5Sr0.5MnO3, we measured the M-Hcurves at tempera-
tures around the TCand the TCO. The inset of Fig. 5shows,
for example, the MHcurves measured at 180 K below TC
and at 150 K below TCO. It can be seen that the hysteretic
losses the area is composed of the increasing and decreasing
field curvesare very large below the TCO, whereas they are
very small or negligible below the TC. To be precise, we have
subtracted the average hysteretic losses from the RC values
calculated without accounting for the hysteretic losses. For
comparison, the results of RC after subtracting the average
hysteretic losses for the case around the TCO are also in-
cluded in Fig. 5. It can be observed in Fig. 5that in the range
of magnetic fields investigated, the RC around the TCis
much larger than that around the TCO. For example, for a
change in magnetic field of 5 T, the RC is 215 J/kg for the
case around the TC, while it is 168 J/kg for the case around
the TCO. This clearly indicates that such hysteretic losses
involved in FOMT significantly reduce the RC and are there-
fore undesirable for an efficient magnetic refrigeration cycle.
An important fact that emerges from the present study is
that the comparison of MCE among magnetocaloric materi-
als by considering the magnitude of SMonly is not ideal.4,5
Instead, a proper estimation should be made with the use of
RC, paying attention to the fact that magnetic hysteresis
losses must be estimated and subtracted from the RC calcu-
lation. In addition, this comparison should be made in the
same temperature range. From a magnetocaloric material
perspective, it is believed that not only FOMT materials but
also SOMT materials are promising candidates for active
magnetic refrigeration applications. Some SOMT materials
with zero hysteretic losses are even more advantageous. An
example of this is Gd—the best magnetic refrigerant candi-
date material to date for sub-room-temperature magnetic
refrigeration.21 Considering the fact that SOMT materials
with a large magnetic entropy change over a broad tempera-
ture range usually possess large RC,13,21 it could be worth-
while to search for enhanced RC in materials that undergo
multiple magnetic phase transitions.2224 From this perspec-
tive, MCE in composite magnetic materials with multiple
SOMTs may be of great interest.22
V. CONCLUSIONS
We have studied the influence of first- and second-order
magnetic phase transitions on the MCE and RC of CO
Pr0.5Sr0.5MnO3. It is shown that while the FOMT at TCO
results in a larger MCE in terms of magnitude, the peak is
confined to a narrow temperature region. The SOMT at TC
yields a smaller MCE with a broader peak spanning a wider
temperature range. This results in a larger value of the RC
around TC, which is more useful for practical applications.
FIG. 4. Color onlineThe method for calculating the RC from the −SMT
curve using Eq. 7for the cases around TCand TCO.
FIG. 5. Color onlineMagnetic field dependence of RC calculated using
Eq. 7for the cases around TCand TCO without and with subtracted hys-
teretic losses. The inset shows the magnetic field dependence of magneti-
zation taken aat 150 K below TCOand bat 180 K below TC.
023909-4 Bingham et al. J. Appl. Phys. 106, 023909 2009
Hysteretic losses accompanying the FOMT are very large
below TCO and therefore detrimental to the RC, whereas they
are negligible below TCdue to the nature of the SOMT. A
proper comparison between magnetocaloric materials should
be made with the use of RC, paying attention to the fact that
magnetic hysteretic losses must be estimated and subtracted
from the RC calculation.
AKNOWLEDGMENTS
The authors acknowledge work at USF supported by
DOE BES Physical Behavior of Materials Program through
Grant No. DE-FG02-07ER46438. H.S. also acknowledges
support from USAMRMC through Grant No. W81XWH-07-
1-0708. Work at UMN supported primarily by DOE Grant
No. DE-FG02-06ER46275and NSF Grant No. DMR-
0804432is also acknowledged.
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023909-5 Bingham et al. J. Appl. Phys. 106, 023909 2009
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Polycrystalline Pr0.48Sr0.52MnO3 forms a tetragonal structure belonging to the I4/mcm space group. X-ray absorption spectroscopy revealed Mn3d level splitting with a higher density of state in $e_{g}\downarrow $ . The temperature-dependent electrical resistivity plot indicates metal-to-insulator transition ( $T_{\mathrm {MI}}$ ) at 224 K at 0 T. Additionally, at lower temperatures, a distinct thermal hysteresis during heating and cooling cycles between 0 and 2 T fields specifies a first-order (FOPT) magnetic phase transition. The temperature-dependent magnetization plot shows a second-order (SOPT) paramagnetic (PM) to ferromagnetic (FM) transition phase transition at 226 K (= $T_{c}$ ) followed by FM to antiferromagnetic (AFM) transition with distinct thermal hysteresis evidence of FOPT at 152.5 K (= $T_{N}$ ). The maximum isothermal entropy change ( $\Delta S_{M}$ ) estimated using Maxwell’s model near SOPT is −3.67 J/kg K at 8 T. Moreover, near FOPT the maximum $\Delta S_{M}$ of value +4.29 J/kg K at $H$ = 4 T is determined, which thereafter remained constant up to 8 T magnetic field. The $\Delta S_{M}$ value at a lower magnetic field is also computed using the phenomenological model. Landau’s theory suitably explains the magnetocaloric (MCE) of Pr0.48Sr0.52MnO3 near SOPT in agreement with the value obtained using Maxwell’s relation.
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In this work, a sample of Pr 0.5 Sr 0.5 MnO 3 nanoparticles with an average crystalline size of < D > = 58 ± 2 nm was prepared by a combination of reactive milling method for 6 h at room temperature and heat treatment at the 1100 °C for 0.5 h. The x-ray diffraction analysis revealed the existence of a Pr 0.5 Sr 0.5 MnO 3 single phase with the tetragonal structure ( I4/mcm space group). Temperature and magnetic field dependences of magnetisation measurements indicated a coexistence of two magnetic phase transitions. One is the antiferromagnetic-ferromagnetic transition at T N = 150 K. The other is the second-order ferromagnetic-paramagnetic phase transition at T C = 273.5 K. Using the modified Arrott plots and the Kouvel-Fisher methods, the critical isotherm analysis, and the scaling relation, the magnetic order in Pr 0.5 Sr 0.5 MnO 3 nanoparticle sample has been pointed out. Accordingly, the critical exponents were found to be β = 0.486, γ = 1.181, and δ = 3.249. These values are quite close to the allowable exponents of the mean field model, suggesting an existence of the long-range ferromagnetic order. A slight deviation from the mean field model has been explained by the formation of the core/shell structure in Pr 0.5 Sr 0.5 MnO 3 nanoparticle.
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In this paper, we present structural, magnetic, magnetocaloric, and critical study of perovskite La 0.7 Ag 0.2 Bi 0.1 MnO 3 (LABMO) nanocrystalline compound synthesized by the sol–gel method. Temperature dependent magnetization measurements reveal the significant suppression of ferromagnetism in the LABMO sample upon Bi-doping on a La-site. The downturn in inverse magnetic susceptibility (χ ⁻¹ ) observed just above T C (236 K) in the paramagnetic regime corroborates the presence of short-range ferromagnetic correlations, which is the characteristic of the Griffith like phase below 270 K. The deviation from linear paramagnetic behavior in χ ⁻¹ implies the strong Griffith singularity. Furthermore, we have employed an integrated Maxwell's thermodynamic relation numerically and used isothermal magnetization data to determine the change in magnetic entropy at various magnetic fields. For a magnetic field change of 5 T, the value of maximum magnetic entropy change is found to be ∼6 J kg ⁻¹ K ⁻¹ . We have also explored the critical behavior of the LABMO sample at transition temperatures using different theoretical models. The value of exponents β, γ, and δ does not fall into any known universality class. Despite this, the scaling relations show that interactions are renormalized around the Curie temperature (T C ). The exponent n ≤ 2 extracted from field dependency on the magnetic entropy change confirms the second-order phase transition in LABMO.
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Introduction Theory Magnetocaloric effect in the phase transition region Methods of investigation of magnetocaloric properties Magnetocaloric effect in 3d metals and their alloys Magnetocaloric effect in amorphous materials Magnetocaloric effect in rare earth metals and their alloys Magnetocaloric effect in intermetallic compounds with rare earth elements Magnetocaloric effect in oxide compounds Magnetocaloric effect in silicides and germanides Magnetocaloric effect in nanosized materials Magnetic refrigeration Conclusions
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In the present work we analyze the magnetic entropy change ΔSM of the Pr1−xCaxMnO3 manganites, for a wide range of Ca concentrations (0.20⩽x⩽0.95). The results for the samples with 0.20<x⩽0.30 present the usual behavior expected for ferromagnetic systems, peaking at the Curie temperature TC. In contrast, for the charge-ordered antiferromagnetic samples (0.30<x<0.90), an anomalous magnetic entropy change starts around the charge-ordering temperature TCO, persisting for lower values of temperature. This effect is associated to a positive contribution to the magnetic entropy change due to the charge-ordering ΔSCO, which is superimposed to the negative contribution from the spin-ordering ΔSspin; that is described using a mean-field approximation. Supposing these contributions, we could also appraise ΔSCOmax as a function of Ca content, which vanishes for the limits x∼0.30 and 0.90 and presents a deep minimum around x∼0.50, with two maxima at x∼0.35 and 0.65. We conclude that for x>0.65 only the magnetic order governs the charge ordering, contrarily to x<0.65, where there are more than one mechanism ruling the charge ordering. Moreover, for the samples with phase coexistence (0.30<x⩽0.40), we found extremely large values for the magnetic entropy change at low temperatures. Finally, for x>0.90, we found usual magnetic entropy change curves, peaking at the Néel temperature TN.
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We report a detailed magnetic, magnetocaloric, and magnetotransport study on R2Ni2Sn compounds with different rare earths. The magnetic state of these compounds is found to be complex because of the coexistence of ferromagnetic and antiferromagnetic components. These compounds show phenomena such as multiple magnetic transitions, nonsaturation of magnetization, and metamagnetic transitions. Analysis of the zero-field heat capacity data shows that the magnetic entropy is less than the theoretical value, indicating the presence of some moment on Ni. Schottky anomaly is present in the magnetic heat capacity data of Sm2Ni2Sn. The temperature variation of magnetocaloric effect reflects the magnetization behavior. Tb2Ni2Sn and to a less extent Gd2Ni2Sn show oscillatory magnetocaloric effect. The variation of magnetocaloric effect is correlated with the ferromagnetic-antiferromagnetic phase coexistence. The electrical resistivity analysis has shown that the electron-magnon scattering is prominent at low temperature, while phonon scattering modified by the s-d interaction is crucial at high temperatures. The magnetoresistance is very large in Ce2Ni2Sn and shows a quadratic dependence on the field, implying the role of spin fluctuations in determining the transport behavior. Large magnetoresistance has been observed in other compounds as well.
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In this work, we report the magnetocaloric effect (∣ΔSM∣), around the charge/orbital ordering transition in the mixed valent manganite Nd0.5Sr0.5MnO3. The magnitude of ∣ΔSM∣ around this first-order transition is around three times larger than that obtained around the second-order transition (ferromagnetic-metallic-to-paramagnetic-insulator) in the same compound. Actually, the magnetocaloric response around the charge-order transition is comparable to pure Gd, the rare earth with the highest magnetocaloric effect. The possibility of an easy tuning of the charge-order transition temperatures in doped manganites opens a way of investigation materials usable in magnetic refrigerators. © 2001 American Institute of Physics.
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We studied three distorted perovskite manganites, Pr{sub 1/2}Sr {sub 1/2}MnO {sub 3} and Nd{sub 1-x}Sr {sub x}MnO{sub 3} with x=1/2 and 0.55 by the neutron diffraction technique. Two samples with x=1/2 exhibit a transition from a ferromagnetic (FM) metal to an antiferromagnetic (AFM) nonmetal. We demonstrate that, in the low temperature phase, Nd{sub 1/2}Sr {sub 1/2}MnO {sub 3} has a CE-type AFM structure with charge ordering, while Pr{sub 1/2}Sr {sub 1/2}MnO {sub 3} and Nd{sub 0.45} Sr{sub 0.55} MnO{sub 3} exhibit an A-type layered AFM structure, but show no clear sign of charge ordering. From the present results, we suggest a possible anisotropy of transport as well as magnetic properties in the A-type AFM structure near x{approximately}1/2. {copyright} {ital 1997} {ital The American Physical Society}
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The relationships between both extensive and intensive properties quantifying the magnetocaloric effect, i.e., between the isothermal entropy change and the adiabatic temperature change, respectively, have been analyzed. An extensive measure of the magnetocaloric effect alone, without considering another important and also extensive thermodynamic property, i.e., the heat capacity, may lead to biased conclusions about the size of the magnetocaloric effect and, consequently, about the applicability of a magnetic material as a magnetic refrigerant. The near room temperature magnetocaloric properties of the colossal magnetoresistive manganites [(R1−xMx)MnO3, where R=lanthanide metal and M is alkaline earth metal] and the recently discovered Fe-based intermetallic material (LaFe11.47Co0.23Al1.3) have been reaccessed and correctly compared with those of the metallic Gd prototype. Our analysis has shown that these 3d materials are inferior to Gd by a factor of 2 or more because of the high values of the heat capacity per unit mass. Also a comparison of the volumetric isothermal entropy change, which is a critical parameter for the operation of a refrigeration unit, indicates that Gd is superior to these 3d materials for practical applications.
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The magnetocaloric effect (MCE) has been observed in three well-defined temperature intervals (region I: 2–115 K, region II: around charge order transition TCO, and region III: around room temperature) in polycrystalline Nd0.5Ca0.5MnO3 (NCMO) manganite system showing a first order (CO) transition at a temperature, TCO ∼ 250 K. The magnitude of ΔSM(H) increases monotonically with applied magnetic field but does not reach saturation even at fields as high as 60 kOe. In the three given temperature regions, negligible magnetic and thermal hysteresis are found, which satisfies the requirements of using NCMO as an effective magnetocaloric material for magnetic refrigeration.
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The magnetocaloric effect in single crystalline Nd0.5Sr0.5MnO3 (NSMO 0.5) is investigated by computing the field dependent entropy change (ΔS) and adiabatic temperature change (ΔTad). At the charge ordering temperature (TCO), the value of ΔSmax is found to be much higher than ΔSmax reported in polycrystalline samples. This “giant” entropy change is attributed to interplay (stronger in single crystals) among spin, charge, lattice, and orbital degrees of freedom resulting in a field induced transition at TCO. In contrast, the change in entropy associated with Curie temperature (TC) is very low. The direct measurements of the field induced temperature change (ΔT) are in agreement with the computed value of ΔS. The presence of short-range correlations with charge/orbital order (COO) above and below TC may be responsible for the suppression of the negative MCE at TC. A critical exponent analysis of the paramagnetic (PM) to ferromagnetic (FM) transition using magnetization data yields mean-field-like values, which is likely to be operative in inhomogeneous systems such as NSMO 0.5 with correlated COO clusters larger than lattice parameter.
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We report a study of the magnetocaloric effect in the ternary alloy system Ni50Mn34In16. This system undergoes an austenite–martensite phase transition, and the change in magnetic entropy is found to be quite large across this martensitic transition. This entropy change is due to an increase in entropy induced by the application of an external magnetic field and can lead to a large inverse magnetocaloric effect. Isothermal magnetic field variation of magnetization exhibits field hysteresis in Ni50Mn34In16 across the martensitic transition. But in spite of the hysteresis losses, a large effective refrigerant capacity can be obtained in this material over a wide temperature interval.
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The magnetocaloric effect in polycrystalline of Pr1 − xSrxMnO3 (x = 0.3, 0.4, 0.5) was investigated. A large magnetic entropy change (7.1 J/kg K) is discovered in Pr0.5Sr0.5MnO3 under a low magnetic field of 1 T at charge-ordered state transition temperature (161 K). The physical mechanism is related to a drastic magnetization change at a temperature where the field-induced magnetic, electron and structural phase transitions occur (from antiferromagnetic charge-ordered state to ferromagnetic charge-disordered state).